Coating compositions stabilized against damage by light, heat and oxygen

ABSTRACT

Coatings comprising 
     A) a binder based on an organic polymer and 
     B) as stabilizer against damage by light, heat and oxygen, a 2-(2′-hydroxyphenyl)-1,3-pyrimidine of the formula I                    
      in which the radicals R 1  to R 6  are as defined in claim  1  have an outstanding resistance to the damaging effects of light, oxygen and heat. Compounds of the formula Ib defined in claim  18  are suitable in general for the stabilization of organic material.

This is a divisional of application Ser. No. 08/665,041, filed Jun. 7,1996, now U.S. Pat. No. 5,753,729, which is a continuation ofapplication Ser. No. 08/241,429, filed May 11, 1994, abandoned.

The invention relates to coating compositions stabilized against damageby light, heat and oxygen, which contain as stabilizer a2-(2′-hydroxyphenyl)-1,3-pyrimidine derivative, to new compounds of the2-(2′hydroxyphenyl)-1,3-pyrimidine type, to their use for stabilizingorganic material and to corresponding compositions.

If it is desired to increase the light stability of an organic material,especially a coating, it is conventional to add a light stabilizer. Oneclass of light stabilizers which is very frequently employed is that ofthe UV absorbers, which protect the material by absorbing the damagingradiation via chromophores. The most commonly used types of UV absorbersare 2-hydroxybenzophenones and 2-(2-hydroxyphenyl)benzotriazoles. Inmore recent literature, triphenyl-triazines are also mentioned asstabilizers for coating materials, for example in the publications U.S.Pat. No. 4,619,956, EP-A-434 608, EP-A-442 847 and EP-A-502 816, or asstabilizers for polycarbonate (U.S. Pat. No. 5,288,778).

Some o-hydroxy-substituted triphenylpyrimidines have also already beenproposed as light stabilizers.

U.S. Pat. No. 3,442,898 describes the protective action of somecompounds of this type against UV radiation in, for example,acetylcellulose, polyamide, polyvinyl chloride and polypropylene.

The teaching of U.S. Pat. No. 4,895,981 comprises their use as lightstabilizers for polyester fibre materials.

Heller and Blattmann, Pure Appl. Chem. 36, 141 (1973) report on the useof some o-hydroxy-substituted triphenylpyrimidines in polyester. Theycome to the conclusion that these compounds, in polyester, have acomparatively small light stabilization effect and contribute to theaccelerated discolouration of the substrate.

It has now been found that certain 2-(2′-hydroxyphenyl)-1,3-pyrimidinederivatives are surprisingly good stabilizers for coating compositions.

The invention relates to a coating composition comprising

A) a binder based on an organic polymer and

B) as stabilizer against damage by light, heat and oxygen, a compound ofthe formula I

 in which

R¹ and R² independently of one another are H; OH; C₁-C₁₂alkyl;cyclohexyl or trifluoromethyl;

R³ and R⁴ independently of one another have one of the definitions of R⁷or are OR⁷ or halogen;

R⁵ has one of the definitions given for R⁷ or is halogen; —O—CO—R¹²;—O—SO₂—R¹³ or —O—R⁷;

R⁶ is H; C₂-C₁₈alkenyl; —X—Z³; benzoyl which is unsubstituted orsubstituted on the phenyl ring by methyl, halogen, —CN or methoxy;—C(Z³)═N—Z³; —CH(Z³)—NH—Z³; a radical of the formula

 or a radical of the formula

R⁷ is hydrogen; C₁-C₁₈alkyl; C₅-C₁₈alkyloxycarbonyl; or C₂-C₁₈alkenyl;or R⁷ is C₁-C₁₈alkyl which is substituted by OH, C₁-C₁₈alkoxy,C₂-C₁₈alkanoyl, C₂-C₈alkenyloxy, halogen, —COOH, —COOR⁸, —CONH₂,—CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹, —CN,—OCOR¹¹, a group of the formula

 and/or phenoxy which is unsubstituted or is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy or halogen; or R⁷ is C₄-C₂₀alkyl which is interrupted by Oand substituted by OH or C₁-C₁₂alkoxy; glycidyl; C₅-C₈cycloalkyl;cyclohexyl which is substituted by OH, C₁-C₄alkyl or —OCOR¹¹; orC₇-C₁₁phenylalkyl which is unsubstituted or substituted by OH, Cl orCH₃;

R⁸ is C₁-C₁₈alkyl; C₂-C₆hydroxyalkyl; C₃-C₁₈alkenyl; C₃-C₂₀alkyl whichis interrupted by O, N or S and/or substituted by OH; C₁-C₄alkyl whichis substituted by —P(O)(OR¹⁴)₂, —N(R⁹)(R¹⁰) or —OCOR¹¹ and/or OH;glycidyl; cyclohexyl or C₇-C₁₁phenylalkyl; or is a group of the formula

R⁹ and R¹⁰ independently of one another are C₁-C₁₂alkyl;C₃-C₁₂alkoxyalkyl; C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl or

R⁹ and R¹⁰ together are C₃-C₉alkylene or -oxaalkylene or -azaalkylene;

R¹¹ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl or phenyl;

R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; phenyl; or —R¹⁵—O—CO—R¹¹; or is agroup of the formula

R¹³ is C₁-C₁₂alkyl; phenyl; naphthyl or C₇-C₁₄alkylphenyl; and

R¹⁴ is C₁-C₁₂alkyl or phenyl;

R¹⁵ is C₁-C₁₈alkylene or C₂-C₁₈alkenylene;

R¹⁶ is hydrogen; oxide; C₁-C₈alkanoyl; C₁-C₁₈alkyl; C₂-C₁₈-hydroxyalkyl;C₃-C₁₈hydroxyalkyl which is interrupted by O; C₁-C₁₈alkoxy;C₅-C₈cycloalkyl; C₅-C₈cycloalkoxy; C₇-C₁₁phenylalkyl; C₇-C₁₁phenylalkylwhich is substituted on the phenyl ring by from 1 to 3 radicalsC₁-C₄-alkyl or C₁-C₈alkanoyl; or C₇-C₁₁phenylalkoxy;

X is a direct bond or —CO—;

Z¹ and Z² independently of one another are C₁-C₁₂alkyl or together areC₄-C₁₀alkylene which may be interrupted by an oxygen atom;

Z³ is C₁-C₂₀-Alkyl; and

Z⁴ is hydrogen or methyl.

A halogen substituent is —F, —Cl, —Br or —I; it is preferably —Cl or—Br, especially —Cl.

In formula I the line protruding into the phenyl ring and carrying thesymbol R⁶ is a substituent which is located at one of the threeremaining free positions, in the o-, m- or p-position to the phenolic OHgroup.

The substituent R⁶ is preferably in the o- or p-position to the phenolicOH group, especially in the p-position.

R⁶ includes, for example, hydrogen, C₁-C₁₂alkyl; C₆-C₁₈alkanoyl;benzoyl; methylbenzoyl; dimethylbenzoyl; benzoyl which is substituted by—Cl, —Br, —CN or —OCH₃; α-methylbenzyl; α,α-dimethylbenzyl;N,N-dialkylaminomethyl; 1-piperidylmethyl; 1-(4-oxapiperidyl)methyl; animide of an acyl radical; and α-(N-alkylamino)alkyl. R⁶ is preferablyhydrogen, C₁-C₆alkyl, benzoyl, α-methylbenzyl, allyl or a radical of theformula

for example hydrogen or C₁-C₆-alkyl or allyl, particularly hydrogen ormethyl and especially hydrogen.

Alkyl R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁶,Z¹ and Z² in the context of the definitions given is branched orunbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl,pentadecyl, hexadecyl,heptadecyl and octadecyl. Alkyl R¹, R², R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴ and R¹⁶ is preferably C₁-C₈alkyl, especiallyC₁-C₄alkyl such as methyl or tert-butyl, in particular methyl.

R⁶ as alkanoyl is, for example, acetyl, propionyl, butyryl, valeryl,caproyl, caprylyl, caprinyl, lauroyl, myristyl, palmitoyl, or stearyl;C₆-C₁₈-alkanoyl is preferred.

Examples of C₁-C₁₈alkoxy R³, R⁴, R⁵ and R¹⁶ are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy,heptoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxyor octadecyloxy; preference is given to C₄-C₁₂alkoxy, for examplen-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octyloxy, 1-ethylhexyloxy,n-nonyloxy and n-decyloxy.

Substituted C₁-C₁₂alkyloxy R³, R⁴ and R⁵ is preferably alkoxyalkyloxy,hydroxyalkyloxy interrupted by O, alkyloxy substituted by

or alkyloxy which is substituted by alkenyloyloxy and/or hydroxyl;particularly interesting examples of R³, R⁴ and R⁵ are—OCH₂CH₂OCOCH═CH₂, —OCH₂CH(OH)C₈H₁₇, —OCH₂CH(OH)C₁₂H₂₅,—OCH₂CH(OH)CH₂OC₈H₁₇, —OCH₂CH(OH)CH₂O—(CH₂₁₂₋₁₄CH₃,—OCH₂CH(OH)CH₂OCOC(CH₃)═CH₂, —OCH₂CH(OH)CH₂OCOCH═CH₂,

R¹, R², R³ and R⁴ are particularly preferably hydrogen or methyl. Ofparticular interest are compounds in which the radicals R¹, R², R³ andR⁴ are identical.

C₃-C₁₈-Alkenyl R⁷, R⁸, R¹¹ and R¹² comprises, inter alia, allyl,isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl,n-octadec-2-enyl and n-octadec-4enyl. For R⁷, R¹¹ and R¹² the definitionof vinyl is also possible. Alkenyl R¹¹ and R¹² is particularlypreferably —CH═CH₂ or —C(CH₃)═CH₂.

Unsubstituted or substituted C₅-C₈cycloalkyl R⁷ is for examplecyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl oracetyloxycyclohexyl; cyclohexyl is preferred.

R¹⁶ is preferably hydrogen, C₁-C₈alkyl, C₂-C₄hydroxyalkyl, C₁-C₁₈alkoxy,C₅-C₈cycloalkoxy or substituted or unsubstituted C₇-C₉phenylalkyl; it isin particular hydrogen, methyl, C₄-C₁₂alkoxy, hydroxyethyl orcyclohexyloxy.

Cycloalkyloxy R¹⁶ is preferably cyclohexyloxy; substituted orunsubstituted C₇-C₁₁phenylalkyl R¹⁶ is preferably benzyl, α-methylbenzylor methylphenyl-methyl.

Where alkyl radicals carry further substituents, or where individualradicals are alkylene, free valencies and bonds to substituents mayextend from the same or from different carbon atoms. Bonds toheteroatoms preferably extend from different carbon atoms.

Consequently, substituted C₁-C₁₂alkyl R⁷ is for example hydroxyalkylsuch as 2-hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl;alkoxyhydroxyalkyl such as 2-hydroxy-3-methoxypropyl,2-hydroxy-3-ethoxypropyl, 2-hydroxy-3-butoxypropyl,2-hydroxy-3-hexoxypropyl or 2-hydroxy-3-(2-ethylhexyloxy)propyl;alkoxycarbonylalkyl such as methoxycarbonylmethyl, ethoxycarbonylmethyl,butoxycarbonylmethyl, octyloxycarbonylmethyl,1-octyloxycarbonyl-1-methylmethyl, 1-octyloxycarbonyl-1-ethylmethyl or1-octyloxycarbonyl-1-hexylmethyl; or alkanoyloxyalkyl oralkenoyloxyalkyl such as 2-(acetyloxy)ethyl, 2-acryloxyethyl or2-methacryloxyethyl; or for example 3-acryloxy- or3-methacryloxy-2-hydroxypropyl.

C₁-C₁₈Alkylene R¹⁵ is for example methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene,hexadecylene, heptadecylene, octadecylene; C₂-C₁₈alkylene orC₄-C₁₂alkenylene is preferred. Particular preference is given toterminal radicals, i.e. the free valencies are located at the ends ofthe longest carbon chain.

Preferred coating compositions are those in which the component (B)employed is a compound of the formula Ia

in which

R³ and R⁴ independently of one another are —H; —OH; C₁-C₁₈alkoxy; —Cl;or —Br or may have one of the definitions of R⁷;

R⁵ has one of the definitions given for R⁷ or is —Cl; —Br; —O—CO—R¹²; or—O—R⁷;

R⁷ is C₁-C₁₈alkyl; or C₃-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which issubstituted by —OH, C₁-C₁₈alkoxy, —COOR⁸, —NHCOR¹¹, —CN, —OCOR¹¹, agroup of the formula

 and/or phenoxy; or R⁷ is C₄-C₂₀alkyl which is interrupted by from 1 to6 —O— and substituted by —OH or C₁-C₁₂alkoxy; glycidyl; C₅-C₈cycloalkyl;or C₇-C₁₁phenylalkyl;

R⁸ is C₁-C₁₈alkyl; C₂-C₆hydroxyalkyl; C₃-C₁₈alkenyl; or is a group ofthe formula

R¹¹ is C₁-C₁₈alkyl or C₂-C₁₈alkenyl;

R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; or —R¹⁵—O—CO—R¹¹; or is a group ofthe formula

R¹⁵ is C₁-C₁₈alkylene or C₄-C₁₈alkenylene; and

R¹⁶ is hydrogen; C₂-C₈alkanoyl; C₁-C₁₂alkyl; C₁-C₁₂alkoxy;C₅-C₈cycloalkyl; C₅-C₈cycloalkoxy; or C₇-C₁₁phenylalkyl.

The compounds of the formula I which are particularly preferably used ascomponent (B) are those in which

R¹ is hydrogen or OH or C₁-C₄alkyl; and R² is hydrogen or C₁-C₄alkyl;

R³ and R⁴ independently of one another are hydrogen or —OH or have oneof the definitions of R⁷ or are OR⁷;

R⁵ has one of the definitions given for R⁷ or is Cl; —Br; —O—CO—R¹²; or—O—R⁷;

R⁶ is hydrogen or C₁-C₆alkyl or allyl;

R⁷ is C₁-C₁₈alkyl; or C₃-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which issubstituted by —OH, C₁-C₁₈alkoxy, —COOR⁸, a group of the formula

 and/or —OCOR¹¹; or R⁷ is C₇-C₁₈alkyl which is interrupted by from 1 to6 —O— and substituted by —OH; C₅-C₈cycloalkyl; or C₇-C₁₁phenylalkyl;

R⁸ is C₁-C₁₈alkyl; C₂-C₆hydroxyalkyl; or C₃-C₁₈alkenyl; or is a group ofthe formula

R¹¹ is C₁-C₁₈alkyl or C₂-C₁₈alkenyl;

R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; —R¹⁵—O—CO—CH═CH₂; or—R¹⁵—O—CO—C(CH₃)═CH₂; or is a group of the formula

R¹⁵ is C₂-C₁₈alkylene; and

R¹⁶ is hydrogen; oxide; C₂-C₈alkanoyl; C₁-C₁₂alkyl; hydroxyethyl;C₁-C₁₂alkoxy; C₅-C₈cycloalkyl; C₅-C₈cycloalkoxy; or C₇-C₁₁phenylalkyl.

Among such compounds, particular preference is given to those in which

R¹ and R² independently of one another are hydrogen or methyl;

R³ and R⁴ independently of one another are hydrogen; methyl; orC₁-C₁₂alkyl which is substituted by —OH, C₁-C₁₈alkoxy, —COOR⁸ and/or—OCOR¹¹; or are C₁-C₁₂alkoxy which is substituted by —OH, C₁-C₈alkoxy,—COOR⁸ and/or —OCOR¹¹;

R⁵ is C₁-C₁₈alkyl; C₃-C₁₈alkenyl; —Cl; —Br; —O—CO—R¹²; or —O—R⁷;

R⁶ is hydrogen or C₁-C₆alkyl or allyl;

R⁷ is C₁-C₁₈alkyl; or C₃-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which issubstituted by —OH, C₁-C₁₈alkoxy, —COOR⁸, a group of the formula

 and/or —OCOR¹¹; or R⁷ is C₇-C₁₈alkyl which is interrupted by from 1 to3 —O— and substituted by —OH;

R¹⁶ is hydrogen; acetyl; C₁-C₈alkyl; C₄-C₁₂alkoxy; C₅-C₈cycloalkyl;C₅-C₈cycloalkoxy; or benzyl.

A particularly emphatic interest is shown in coating compositionscomprising as component (B) a compound of the formula I in which R¹ andR² independently of one another are hydrogen or methyl; R³ and R⁴independently of one another are hydrogen, methyl or methoxy and R⁶ ishydrogen.

Of outstanding interest as component (B) are compounds of the formula Iin which

R¹ and R² are identical and are hydrogen or methyl;

R³ and R⁴ are identical and are hydrogen or methyl or methoxy;

R⁵ is —O—R⁷;

R⁶ is hydrogen;

R⁷ is C₁-C₁₈alkyl; or R⁷ is C₁-C₁₂alkyl which is substituted by —OH,C₁-C₁₈alkoxy, —COOR⁸, —OCOR¹¹ and/or a group of the formula

R⁸ is C₁-C₁₂alkyl; and

R¹¹ is C₁-C₁₂alkyl.

The coating composition according to the invention preferably comprises0.01-10 parts by weight of B, in particular 0.05-10 parts by weight of Band especially 0.1-5 parts by weight of B per 100 parts by weight ofsolid binder A.

A suitable binder (component A) may in principle be any of those commonin industry, for example those as described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Ed., Vol. A18, pp. 368-426, VCH, Weinheim1991. In general it is a film-forming binder based on a thermoplastic orthermosettable resin, predominantly on a thermosettable resin. Examplesof these are alkyd, acrylic, polyester, phenolic, melamine, epoxy andpolyurethane resins and mixtures thereof.

Component A may be a cold-curable or a heat-curable binder; the additionof a curing catalyst may be advantageous. Examples of catalysts suitablefor accelerating the curing of the binder are described in Ullmann'sEncyclopedia of Industrial Chemistry, Vol. A 18, p. 469, VCHVerlagsgesellschaft, Weinheim 1991.

Preferred coating compositions are those in which component A is abinder comprising a functional acrylate resin and a crosslinking agent

Examples of coating compositions containing specific binders are:

1. coating materials based on cold- or hot-crosslinkable alkyd,acrylate, polyester, epoxy or melamine resins or mixtures of theseresins, with or without the addition of a curing catalyst;

2. two-component polyurethane coating materials based on hydroxylgroup-containing acrylate, polyester or polyether resins and aliphaticor aromatic polyisocyanates;

3. one-component polyurethane coating materials based on blockedpolyisocyanates which are deblocked during the baking procedure;

4. two-component coating materials based on (poly)ketimines andaliphatic or aromatic polyisocyanates;

5. two-component coating materials based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester,

6. two-component coating materials based on carboxyl or aminogroup-containing polyacrylates and polyepoxides;

7. two-component coating materials based on anhydride group-containingacrylate resins and a polyhydroxy or polyamino component;

8. two-component coating materials based on (poly)oxazolines andanhydride group-containing acrylate resins or unsaturated acrylateresins or aliphatic or aromatic polyisocyanates;

9. two-component coating materials based on unsaturated polyacrylatesand polymalonates;

10. thermoplastic polyacrylate coating materials based on thermoplasticacrylate resins or acrylate resins which crosslink under the action ofexternal crosslinking agents, in combination with etherified melamineresins;

11. coating systems based on siloxane-modified or fluorine-modifiedacrylate resins.

The coating compositions according to the invention may also beradiation-curable coating compositions. In this case the binderessentially comprises monomeric or oligomeric compounds havingethylenically unsaturated bonds, which are cured after application by UVradiation or electron beams, i.e. are converted into a crosslinked, highmolecular weight form. Corresponding systems are described in theabovementioned publication, Ullmann's Encyclopedia of IndustrialChemistry, 5th Ed., Vol. A18, pages 451-453. In radiation-curablecoating compositions the compounds of the formula I may also be employedwithout the addition of sterically hindered amines.

The coating composition according to the invention preferablycontains—in addition to components A and B—as component C, a lightstabilizer of the sterically hindered amine and/or2-hydroxyphenyl-2H-benzotriazole type, such as, for example, those givenin the list below under headings 2.1 and 2.6.

In order to achieve maximum light resistance, the addition of stericallyhindered amines as given in the stated list under 2.6, is of specialadvantage. The invention therefore also relates to a coating compositionwhich contains in addition to components A and B, as component C, alight stabilizer of the sterically hindered amine type.

It is preferably a 2,2,6,6-tetraalkylpiperidine derivative whichcontains at least one group of the formula

in which R is hydrogen or methyl, especially hydrogen.

Component C is preferably used in a quantity of 0.05-5 parts by weightper 100 parts by weight of the solid binder.

Examples of tetraalkylpiperidine derivatives which can be used ascomponent C are given in U.S. Pat. No. 5,073,278; of special importanceare those listed in columns 3-21 under sections a) to f). The sectionsof this patent document indicated are considered part of thisdescription. It is particularly expedient to employ the followingtetraalkylpiperidine derivatives:

bis(2,2,6,6-tetramethylpiperid-4-yl)succinate,

bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,

bis(1,2,2,6,6-pentamethylpiperid-4yl)sebacate,

di(1,2,2,6,6-pentamethylpiperid-4-yl)butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,

bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)sebacate,

tetra(2,2,6,6-tetramethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,

tetra(1,2,2,6,6-pentamethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,

2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,

8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione,

or a compound of the formulae

where m is 5-50.

In addition to components A and B, the coating composition may alsocontain further components, for example solvents, pigments, dyes,plasticizers, stabilizers, thixotropic agents, drying catalysts and/orlevelling assistants. Examples of possible components are thosedescribed in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed.,Vol. A18, pp. 429-471, VCH, Weinheim 1991.

Examples of possible drying catalysts or curing catalysts areorganometallic compounds, amines, resins containing amino groups, and/orphosphines. Organometailic compounds are, for example, metalcarboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu,or metal chelates, especially those of the metals Al, Ti or Zr, ororganometallic compounds such as organotin compounds.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, theoctanoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates.

Examples of metal chelates are the aluminium, titanium or zirconiumchelates of acetylacetone, ethyl acetoacetate, salicylaldehyde,salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetoacetateand the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctanoate.

Examples of amines are in particular tertiary amines such astributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and their salts. Other examplesare quaternary ammonium salts, for example trimethylbenzylammoniumchloride.

Resins containing amino groups are simultaneously binder and curingcatalyst. Examples of these are acrylate copolymers which contain aminogroups.

The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

The coating compositions according to the invention can be applied toany desired substrates, for example to metal, wood, plastic or ceramicmaterials. They are preferably used as topcoat in the finishing of cars.If the topcoat consists of two coats, the bottom coat being pigmentedand the upper coat being non-pigmented, then the coating compositionaccording to the invention can be used for the upper or the bottom coator for both coats, but preferably for the upper coat.

The coating compositions according to the invention can be applied tothe substrates by the conventional methods, for example by brushing,spraying, flowcoating, dipping or electrophoresis; see also Ullmann'sEncyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 491-500.

Depending on the binder system the coatings can be cured at roomtemperature or by heating. The coatings are preferably cured at 50-150°C.; higher temperatures may be employed for powder coatings.

The coatings obtained in accordance with the invention have anoutstanding resistance to the damaging effects of light, oxygen andheat; in particular, reference should be made to the good lightfastnessand weathering resistance of the resulting coatings, for example paints.

The invention therefore relates also to a coating, in particular avarnish, which is stabilized by containing the compound of the formula Iaccording to the invention against damaging effects of light, oxygen andheat. The varnish is preferably a topcoat for cars. The invention alsorelates to a method of stabilizing a coating based on organic polymersagainst damage by light, oxygen and/or heat, which comprises admixingwith the coating composition a compound of the formula I, and to the useof compounds of the formula I in coating compositions as stabilizersagainst damage by light, oxygen and/or heat.

In a further embodiment of the method, the binders used are those inwhich a compound of the formula I is incorporated by copolymerization orcopolycondensation. Compounds suitable for this purpose are those of theformula I in which the radical R⁵ contains a copolymerizable,ethylenically unsaturated group or a functional group suitable forcopolycondensation. In this case the coating composition can onlycomprise component A.

The coating compositions usually contain an organic solvent or solventmixture in which the binder is soluble. The coating composition may,however, also be an aqueous solution or dispersion. The vehicle may alsobe a mixture of an organic solvent and water. The coating compositionmay also be a high-solids coating or can be solvent-free (powdercoating).

The pigments can be inorganic, organic or metallic pigments. The coatingcompositions according to the invention preferably contain no pigmentsand are used as clearcoat.

A likewise preferred use of the coating composition is as a topcoat forapplications in the automotive industry, especially as the pigmented ornon-pigmented topcoat of the coating system. However, its use forunderlying layers is also possible.

Some of the compounds of the formula I described above as component (B)are new compounds. The invention consequently also relates to compoundsof the formula Ib

in which

R¹ and R² independently of one another are H; OH; C₁-C₁₂alkyl;cyclohexyl or trifluoromethyl;

R³ and R⁴ independently of one another are hydrogen; —OH; C₁-C₃alkyl;C₁-C₃alkoxy; or halogen or have one of the definitions of R⁷ or are OR⁷;

R⁵ has one of the definitions given for R⁷ or is halogen; C₁-C₃alkyl;—O—CO—R¹²; —O—SO₂—R¹³ or —O—R⁷;

R⁶ is H; C₂-C₁₈alkenyl; —X—Z³; benzoyl which is unsubstituted orsubstituted on the phenyl ring by methyl, halogen, —CN or methoxy;—C(Z³)═N—Z³; —CH(Z³)—NH—Z³; a radical of the formula

 or a radical of the formula

R⁷ is C₄-C₁₈alkyl or C₂-C₁₈alkenyl or C₅-C₁₈alkyloxycarbonyl; or R⁷ isC₁-C₁₈alkyl which is substituted by OH, C₁-C₁₈alkoxy, C₂-C₁₈alkanoyl,halogen, —COOH, —COOR⁸, —CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH_(2,) —NHR⁹,—N(R⁹)(R¹⁰), —NHCOR¹¹, —CN, —OCOR¹¹, a group of the formula

 and/or phenoxy which is unsubstituted or is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy or halogen; or R⁷ is C₄-C₂₀alkyl which is interrupted by Oand substituted by OH or C₁-C₁₂alkoxy; glycidyl; C₅-C₈cycloalkyl;cyclohexyl which is substituted by OH, C₁-C₄alkyl or —OCOR¹¹; orC₇-C₁₁-phenylalkyl which is unsubstituted or substituted by OH, Cl orCH₃;

R⁸ is C₁-C₁₈alkyl; C₂-C₆hydroxyalkyl; C₃-C₁₈alkenyl; C₃-C₂₀alkyl whichis interrupted by O, N or S and/or substituted by OH; C₁-C₄alkyl whichis substituted by —P(O)(OR¹⁴)₂, —N(R⁹)(R¹⁰) or —OCOR¹¹ and/or OH;glycidyl; cyclohexyl or C₇-C₁₁phenylalkyl; or is a group of the formula

R⁹ and R¹⁰ independently of one another are C₁-C₁₂alkyl;C₃-C₁₂alkoxyalkyl; C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl or

R⁹ and R¹⁰ together are C₃-C₉alkylene or -oxaalkylene or -azaalkylene;

R¹¹ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl or phenyl;

R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; phenyl; or —R¹⁵—O—CO—R¹¹; or is agroup of the formula

R¹³ is C₁-C₁₂alkyl; phenyl; naphthyl or C₇-C₁₄alkylphenyl; and

R¹⁴ is C₁-C₁₂alkyl or phenyl;

R¹⁵ is C₁-C₁₈alkylene or C₂-C₁₈alkenylene;

R¹⁶ is hydrogen; oxide; C₁-C₈alkanoyl; C₁-C₁₈alkyl; C₂-C₁₈hydroxyalkyl;C₃-C₁₈hydroxyalkyl which is interrupted by O; C₁-C₁₈-alkoxy;C₅-C₈cycloalkyl; C₅-C₈-cycloalkoxy; C₇-C₁₁phenylalkyl; C₇-C₁₁phenylalkylwhich is substituted on the phenyl ring by from 1 to 3 radicalsC₁-C₄alkyl or C₁-C₈alkanoyl; or C₇-C₁₁phenylalkoxy;

X is a direct bond or —CO—;

Z¹ and Z² independently of one another are C₁-C₁₂alkyl or together areC₄-C₁₀alkylene which may be interrupted by an oxygen atom;

Z³ is C₁-C₂₀-Alkyl; and

Z⁴ is hydrogen or methyl;

with the exception of a compound of the formula I in which 2 of theradicals R³, R⁴ and R⁵ are alkoxy and the third radical has a definitionother than alkoxy.

The preferred definitions of the radicals to R¹ to R¹⁶ in the compoundsof the formula Ib are essentially the same as those for thecorresponding radicals in the compounds of the formula I.

In compounds of the formula Ib, R¹, R², R³ and R⁴ independently of oneanother are preferably H, C₁-C₄alkoxy or C₁-C₄alkyl, especially H ormethyl.

R⁵ in compounds of the formula Ib is preferably —O—R⁷.

Preferred compounds of the formula Ib are those in which

R¹ and R² independently of one another are H; OH; C₁-C₁₂alkyl;cyclohexyl or trifluoromethyl;

R³ and R⁴ independently of one another are hydrogen; —OH; C₁-C₁₈alkyl;C₁-C₁₈alkoxy; or halogen or may have one of the definitions of R⁷;

R⁵ has one of the definitions given for R⁷ or is halogen; —O—CO—R¹²;—O—SO₂—R¹³ or —O—R⁷;

R⁶ is H or C₁-C₁₂alkyl;

R⁷ is C₂-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which is substituted by OH,C₁-C₁₈alkoxy, halogen, —COOH, —COOR⁸, —CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰),—NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹, —CN, —OCOR¹¹ and/or phenoxy which isunsubstituted or is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen;or R⁷ is C₄-C₂₀alkyl which is interrupted by one or more O andsubstituted by OH or C₁-C₁₂alkoxy; glycidyl; C₅-C₈cycloalkyl; cyclohexylwhich is substituted by OH, C₁-C₄alkyl or —OCOR¹¹; or C₇-C₁₁phenylalkylwhich is unsubstituted or substituted by OH, Cl or CH₃;

R⁸ is C₁-C₁₈alkyl; C₂-C₆hydroxyalkyl; C₃-C₁₈alkenyl; C₃-C₂₀alkyl whichis interrupted by O, N or S and/or substituted by OH; C₁-C₄alkyl whichis substituted by —P(O)(OR¹⁴)₂, —N(R⁹)(R¹⁰) or —OCOR¹¹ and/or OH;glycidyl; cyclohexyl or C₇-C₁₁phenylalkyl;

R⁹ and R¹⁰ independently of one another are C₁-C₁₂alkyl;C₃-C₁₂alkoxyalkyl; C₄-C₁₆-dialkylamninoalkyl or C₅-C₁₂cycloalkyl or

R⁹ and R¹⁰ together are C₃-C₉alkylene or -oxaalkylene or -azaalkylene;

R¹¹ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl or phenyl;

R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; phenyl; or —R¹⁵—O—CO—R¹¹; or is agroup of the formula

R¹³ is C₁-C₁₂alkyl; phenyl; naphthyl or C₇-C₁₄alkylphenyl; and

R¹⁴ is C₁-C₁₂alkyl or phenyl;

R¹⁵ is C₁-C₁₈alkylene or C₂-C₁₈alkenylene;

R¹⁶ is hydrogen; C₁-C₈alkanoyl; C₁-C₁₈alkyl; C₁C₁₈alkoxy;C₅-C₈cycloalkyl; C₅-C₈cycloalkoxy; C₇-C₁₁phenylalkyl; C₇-C₁₁phenylalkylwhich is substituted on the phenyl ring by from 1 to 3 radicalsC₁-C₄alkyl or C₁-C₈alkanoyl; or C₇-C₁₁phenylalkoxy; and

X is a direct bond or —CO—.

Particularly preferred compounds of the formula Ib are those in which

R¹ and R² independently of one another are hydrogen or C₁-C₄alkyl;

R³ and R⁴ independently of one another are hydrogen; C₁-C₃alkyl;C₁-C₃alkoxy or halogen or have one of the definitions of R⁷ or are OR⁷;

R⁵ has one of the definitions given for R⁷ or is halogen; —O—CO—R¹² or—O—R⁷;

R⁶ is in the o-position to R⁵ and in the p-position to —OH and ishydrogen, C₁-C₆alkyl, allyl, C₆-C₁₈alkanoyl, benzoyl or α-methylbenzyl;

R⁷ is C₄-C₁₈alkyl or C₂-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which issubstituted by OH, C₁-C₁₈alkoxy, —COOR⁸, a group of the formula

 and/or —OCOR¹¹; or R⁷ is C₇-C₁₈alkyl which is interrupted by from 1 to6 —O— and substituted by OH; C₅-C₈cycloalkyl; or C₇-C₁₁phenylalkyl;

R⁸ is C₁-C₁₈alkyl; C₃-C₁₈alkenyl or a group of the formula

R¹¹ is C₁-C₁₈alkyl or C₂-C₁₈alkenyl;

R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; —R¹⁵—O—CO—CH═CH₂; or—R¹⁵—O—CO—C(CH₃)═CH₂; or is a group of the formula

R¹⁵ is C₂-C₁₈alkylene; and

R¹⁶ is hydrogen; oxide; C₂-C₈alkanoyl; C₁-C₁₂alkyl; hydroxyethyl;C₁-C₁₈alkoxy; C₅-C₈cycloalkyl; C₅-C₈cycloalkoxy; or C₇-C₁₁phenylalkyl.

Among these, compounds of emphatic significance are those in which

R¹ and R² independently of one another are hydrogen or C₁-C₄alkyl;

R³ and R⁴ independently of one another are hydrogen or C₁-C₄alkoxy orC₁-C₄alkyl;

R⁵ is —O—R⁷;

R⁶ is in the o-position to R⁵ and in the p-position to OH and ishydrogen or C₁-C₆alkyl or allyl;

R⁷ is C₄-C₁₈alkyl or C₃-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which issubstituted by OH, C₁-C₁₈alkoxy, —COOR⁸, a group of the formula

 and/or —OCOR¹¹;

R⁸ is C₁-C₁₈alkyl; and

R¹¹ is C₁-C₁₈alkyl or C₂-C₃alkenyl.

The compounds of the formula I, Ia and Ib can be prepared incorrespondence with or in analogy to one of the methods indicated inU.S. Pat. No. 3,442,898, by Friedel-Crafts addition of halopyrimidinesonto appropriate phenols.

This is advantageously carried out by reacting one equivalent of acompound of the formula (A)

in which R′ and R″ independently of one another are each

in which R¹ is not hydroxyl, with the quantity of equivalents of thecorresponding phenol of the formula (B)

and, if desired, of the formula (C)

as there are chlorine atoms in formula (A).

Where different phenols are reacted, the overall reaction is preferablycarried out over two or more stages, so that initially one phenol isreacted with the compound of the formula (A), the reaction product isthen reacted with another phenol, and the product resulting therefrom isreacted if appropriate with the third phenol. If the end product of theformula I, Ia or Ib is derived, for example, fromtriresorcinylpyrimidine, then, in accordance with the indications inU.S. Pat. No. 3,442,898, 2,4,6-trichloropyrimidine as the compound ofthe formula (A) can be reacted in one stage with resorcinol as thecompound of the formula (B).

The starting materials are reacted in a manner known per se by reactingthem in an inert solvent in the presence of anhydrous AlCl₃. Aluminiumtrichloride and phenol are in this case advantageously employed inexcess; for example, aluminium trichloride can be used in a 5-15% molarexcess and the phenol in a 1-30%, in particular in a 5-20%, molarexcess. Where the compound of the formula (A) contains 1 chlorine atom,1-1.3 mol, for example, of compound (B) per mole of compound (A) can beemployed for the reaction; where the compound of the formula (A)contains 2 or 3 chlorine atoms, then generally the two-fold orthree-fold quantity of phenol is used.

Examples of suitable solvents are hydrocarbons, chlorinated hydrocarbonsor nitrated aromatic hydrocarbons; high-boiling hydrocarbons arepreferred, such as ligroin, toluene or xylene. The temperature is ingeneral not critical; the temperatures usually employed are between 20°C. and the boiling point of the solvent, for example between 50° C. and150° C. The product can be worked up by common methods, for example byfiltration and drying; if required, further purification steps such asrecrystallization can be carried out.

Free phenolic hydroxyl groups of the reaction product, especially in thep-position to the pyrimidine ring, can subsequently be etherified oresterified in a known manner; cf. also U.S. Pat. No. 3,442,898. For thepreparation of the phenol ethers, the free phenols are preferablyreacted with epoxides or halides, especially with glycidyl compounds orappropriate chlorides or bromides.

The starting compounds of the formula (A) are known or can be preparedby known methods or in analogy to the known compounds.

Examples of possible starting compounds are the knownamino-aryl-pyrimidines, whose synthesis is described, inter alia, by D.Simon et al., J. Heterocyclic Chem. 22, 1551 (1985).

The exchange of amino on the pyrimidine ring for —OH, and also theexchange of hydroxyl for halogen to form the halopyrimidines, isdescribed in, for example, D. J. Brown and P. Waring, Austr. J. Chem.26, 443 (1973) and U.S. Pat. No. 3,442,898.

A further method for the preparation of starting compounds of theformula (A) in which at least one of the substituents R′ and R″ is not—Cl is the reaction of 2,4,6-trichloropyrimidine with a correspondinglysubstituted phenylmagnesium halide (Grignard reaction). The reaction canlikewise be carried out in a known manner, by first reacting a compoundof the formula

in which X′ is Cl or Br with metallic magnesium in an ether, for examplein diethyl ether or in tetrahydrofuran (THF), in order to prepare thephenylmagnesium halide. This reagent is then reacted with2,4,6-trichloropyrimidine to give the compound of the formula (A),preferably with the exclusion of oxygen and moisture. The subsequentwork-up can in turn be carried out in a known manner, for example bydilution with an organic solvent, such as toluene, hydrolysis of theresidual phenylmagnesium halide with aqueous HCl, and separation, dryingand concentration of the organic phase.

Some of the compounds obtained of the formula (A) are new compoundswhich are likewise a subject of the invention. These are compounds ofthe formula (A′)

in which R¹ is H; C₁-C₁₂alkyl; cyclohexyl or trifluoromethyl; and R^(3′)is C₁-C₁₈alkyl; C₁-C₁₈alkoxy; C₂-C₁₈alkenyl; halogen; C₃-C₁₈alkoxy whichis interrupted by —O—; or cyclohexyl. Among these, those compounds offormula (A′) are preferred in which R^(1′) is hydrogen or C₁-C₄alkyl andR^(3′) is C₁-C₁₈alkyl or C₁-C₁₈ alkoxy or Cl, for example C₁-C₄alkyl orC₁-C₄alkoxy or Cl, especially methyl, methoxy or Cl.

The compounds of the formula Ib according to the invention can be usedas stabilizers for organic materials against damage by light, oxygen orheat. The compounds according to the invention are especially suitableas light stabilizers.

Examples of the materials to be stabilized are oils, fats, waxes,cosmetics, biocides or photographic materials. A utility of particularinterest is in polymeric materials, for example in plastics, rubbers,paints or adhesives. Examples of polymers and other substrates which canbe stabilized in this way are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epi-chlorohydrin homo- andcopolymers, especially polymers of halogen-containing vinyl compounds,for example polyvinyl chloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof such asvinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate orvinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer, polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

The invention therefore also relates to a composition comprising

A) an organic material which is sensitive to damage by light, oxygenand/or heat, and

B) as stabilizer, a compound of the formula Ib.

The compounds of the formula Ib according to the invention can beemployed with particular advantage in compositions which contain ascomponent A a synthetic organic polymer, especially a thermoplasticpolymer or a photographic material. Examples of suitable thermoplasticpolymers are polyolefins and polymers which contain heteroatoms in theprincipal chain. Preferred compositions are those in which component Ais a photographic material or a thermoplastic polymer which containsnitrogen, oxygen and/or sulfur, especially nitrogen or oxygen, in theprincipal chain.

Polymers which contain heteroatoms in the principal chain are inparticular polymers containing O, S and/or N. Examples of such polymersare the following classes of thermoplastic polymers:

1. Polyacetals, such as polyoxymethylene, and those polyoxymethyleneswhich contain comonomers such as, for example, ethylene oxide;polyacetals which are modified with thermoplastic polyurethanes,acrylates or MBS.

2. Polyphenylene oxides and polyphenylene sulfides and mixtures thereofwith styrene polymers or polyamides.

3. Polyamides and copolyamides, for example those derived from diaminesand dicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactones, such as polyamide 4, polyamide 6, polyamide 6/6,6/10, 6/9, 6/12, 4/6, polyamide 11, polyamide 12, aromatic polyamidesbased on m-xylene, diamine and adipic acid; polyamides prepared fromhexamethylenediamine and iso- and/or terephthalic acid and, if desired,an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethyleneterephthalamide,poly-m-phenyleneisophthalamide; block copolymers of the abovementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, for example withpolyethylene glycol, polypropylene glycol or polytetramethylene glycol;additionally, polyamides or copolyamides modified with EPDM or ABS; andpolyamides condensed during processing (RIM polyamide systems).

4. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

5. Polyesters, for example those derived from dicarboxylic acids anddialcohols and/or from hydroxycarboxylic acids or the correspondinglactones, such as polyethylene terephthalate, polybutyleneterephthalate, poly-1,4-dimethylolcyclohexane terephthalate,polyhydroxybenzoates, and block polyether-esters derived from polyethershaving terminal hydroxyl groups; also, polyesters modified withpolycarbonates or MBS.

6. Polycarbonates and polyester carbonates, especially aromaticpolycarbonates such as those based on 2,2-bis(4-hydroxyphenyl)propane or1,1-bis(4-hydroxyphenyl)cyclohexane.

7. Polysulfones, polyether sulfones and polyether ketones, especiallyaromatic polymers from this class.

8. Mixtures (polyblends) of these polymers with one another or withother polymers, for example with polyolefins, polyacrylates, polydienesor other elastomers as impact modifiers.

Preferred among these are the polycarbonates, polyesters, polyamides,polyacetals, polyphenylene oxides and polyphenylene sulfides, butespecially the polycarbonates. This should be understood as referring inparticular to those polymers whose constitutional repeating unit is ofthe formula

in which A is a divalent phenolic radical. Examples of A are given,inter alia, in U.S. Pat. No.4,960,863 and DE-A-3 922 496. A may, forexample be derived from hydroquinone, resorcinol, fromdihydroxybiphenyls or bisphenols in the broadest sense such asbis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes,bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers,bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones,bis(hydroxyphenyl)sulfoxides,α,α′-bis(hydroxyphenyl)diisopropylbenzenes, for example from thecompounds 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)cyclohexane or from the compounds of theformulae

Other compositions of interest are those in which component (A) is apolyolefin, for example polyethylene or polypropylene.

The invention also relates to a method of stabilizing organic materialagainst damage by light, oxygen and/or heat, which comprises adding tothis material a compound of the formula Ib as stabilizer, and to the useof compounds of the formula Ib for stabilizing organic material.

The quantity of stabilizer to be used depends on the organic material tobe stabilized and on the intended use of the stabilized material. Ingeneral, the composition according to the invention contains from 0.01to 15, in particular from 0.05 to 10 and especially from 0.1 to 5 partsby weight of the stabilizer (component B) per 100 parts by weight ofcomponent A.

Incorporation into the organic polymers, for example into the syntheticorganic and, in particular, thermoplastic polymers can be effected byadding the compounds according to the invention and, if desired, otheradditives by the methods conventional in industry. Incorporation can beeffected advantageously before or during shaping, for example by mixingthe pulverulent components or by adding the stabilizer to the melt orsolution of the polymer, or by applying the dissolved or dispersedcompounds to the polymer, followed if desired by the evaporation of thesolvent. In the case of elastomers, these may also be stabilized aslatices. A further possibility for incorporating the compounds accordingto the invention into polymers consists in their addition before orduring the polymerization of the corresponding monomers or beforecrosslinking.

The compounds according to the invention or mixtures thereof can also beadded to the plastics to be stabilized in the form of a masterbatchwhich contains these compounds in, for example, a concentration of from2.5 to 25% by weight.

The compounds according to the invention are advantageously incorporatedby the following possible methods:

as emulsion or dispersion (e.g. to latices or emulsion polymers)

as a dry mixture during the mixing of additional components or polymermixtures

by direct addition to the processing apparatus (e.g. extruder, internalmixer etc.)

as solution or melt.

The resulting stabilized polymer compositions can be converted, by theconventional methods such as hot pressing, spinning, extrusion orinjection moulding, into shaped articles such as fibres, films, strips,plates, webbed plates, vessels, pipes and other profiles.

The invention therefore also relates to the use of the polymercomposition according to the invention for the production of a shapedarticle.

The utility of the compositions in multilayer systems is also ofinterest. In this case a polymer composition according to the inventionhaving a relatively high content of stabilizer of the formula Ib, forexample 5-15% by weight, is applied in a thin layer (10-100 μm) to ashaped article made from a polymer which contains little or nostabilizer of the formula Ib. Application can be carried outsimultaneously with the shaping of the basic structure, for example byso-called coextrusion. The composition can also be applied, however, tothe ready-formed basic structure, for example by lamination with a filmor by coating with a solution. The external layer of layers of thefinished article have the function of a UV filter which protects theinterior or the article inside against UV light. The external layerpreferably contains 5-15% by weight, in particular 5-10% by weight, ofat least one stabilizer of the formula Ib.

The use of the polymer composition according to the invention for theproduction of multilayer systems, where the external layer(s) comprise apolymer composition according to the invention in a thickness of 10-100μm whereas the inner layer contains little or no stabilizer of theformula Ib, is therefore a further subject of the invention.

The use of a polymer composition according to the invention in whichcomponent A is a polycarbonate for the production of multilayer systemsis of particular interest.

The polymers stabilized in this way are distinguished by high resistanceto weathering and especially by high resistance to UV light. By thismeans they show long-term retention, even when used outdoors, of theirmechanical properties and their colour and gloss.

The stabilizer (component B) may also be a mixture of two or morecompounds according to the invention. The organic materials, stabilizedcoating compositions or compositions according to the invention may alsocontain, in addition to the stabilizer of the formula I, Ia or Ib, otherstabilizers or other additives, for example antioxidants, further lightstabilizers, metal deactivators, phosphites or phosphonites. Examples ofthese are the following stabilizers:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-di-methyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thio-bis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylene-bis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tris-(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis-[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV absorbers and light stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,mixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyl-oxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonyl-ethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃₂, whereR═3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoxnimes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-piperidyl)succinate,bis(1,2,2,6,6-pentamethylpiperidyl)sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazasprio[4.5]decan-2,4-dion,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphsophite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6methylphenyl)ethylphosphite.

5. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

6. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

8. Nucleating agents, for example, 4-tert-butylbenzoic acid, adipicacid, diphenylacetic acid.

9. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

10. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, antistatic agentsand blowing agents.

11. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, DE-A-4316 611, DE-A4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The nature and quantity of the further stabilizers added depends on thenature of the substrate to be stabilized and on its intended use; inmany cases from 0.1 to 5% by weight is used, based on the polymer to bestabilized.

A further subject of the present invention is the use of a compound ofthe formula Ib in photographic materials as a stabilizer against damageby light, especially damage by UV light, and the photographic materialcomprising a compound of the formula Ib, with mixtures of compounds ofthe formula Ib also being relevant.

The compounds according to the invention can be used for all types ofphotosensitive material. They can be employed, for example, for colourpaper, colour reversal paper, direct positive colour material, colournegative film, colour positive film, colour reversal film and others.They are preferably used inter alia for photosensitive colour materialwhich contains a reversal substrate or which forms positives.

The compounds according to the invention can also be combined with otherUV absorbers, especially those which are dispersible in aqueous gelatin,for example with hydroxyphenylbenzotriazoles (cf. for example U.S. Pat.Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones,oxanilides, cyanoacrylates, salicylic esters, acrylonitriles orthiazolines. It is advantageous here for these other UV absorbersdissolved in oil to be employed in different layers of the photographicmaterial than the UV absorbers according to the invention. Photographicmaterials which can be stabilized with particularly good success arematerials similar to those described in U.S. Pat. No. 4,518,686.

The present application therefore relates to photographic materialcomprising, on a support, a blue-sensitive, a green-sensitive and/or ared-sensitive silver halide emulsion layer and, if desired, a protectivelayer, with a layer containing a UV absorber being arranged above thetopmost silver halide emulsion layer, which UV absorber is of theformula Ib.

In a further embodiment, the material according to the inventioncomprises a layer containing a UV absorber of the formula Ib which isarranged between the green-sensitive and the red-sensitive silver halideemulsion layer, a further layer containing a UV absorber of the formulaIb being able to be arranged above the topmost silver halide emulsionlayer.

Good results are also obtained if the UV absorber of the formula Ib isadditionally contained in the red-sensitive silver halide emulsionlayer.

Other preferred photographic materials are those which have a layercomprising a compound of the formula Ib above the topmost silver halideemulsion layer and/or between the green-sensitive and the red-sensitivesilver halide emulsion layer, an oil-soluble UV absorber additionallybeing contained in a layer which contains no UV absorber of the formulaIb.

Furthermore, it may be advantageous for all or some of the said layerswhich can contain a UV absorber to contain a UV absorber of the formulaIb and/or a further UV absorber which is dispersible in aqueous gelatin,but where it is necessary for a UV absorber of the formula Ib to becontained in at least one layer. The material according to the inventionpreferably contains gelatin interlayers between the silver halideemulsion layers.

Preferred photographic materials of this kind are those in which thesilver halide in the blue-sensitive, green-sensitive and/orred-sensitive layer is silver chloride bromide, at least 90 mol % ofwhich consists of silver chloride.

Further preferred photographic materials are those which contain thesilver halide emulsion layers in the sequence blue-sensitive,green-sensitive and red-sensitive silver halide emulsion layer.

In relation to materials containing benzotriazole UV absorbers, thephotographic materials according to the invention offer the advantagethat the UV absorbers of the formula Ib are required in a comparativelysmall quantity to give sufficient protection against UV radiation. Thismeans that the thickness of the layers in which the UV absorbers of theformula Ib are incorporated can be very thin, which has a positiveeffect on, for example, the distinctness of the images produced usingthis material.

Yellow couplers which can be used in the material according to theinvention are preferably compounds of the formula A

in which R₁ is alkyl or aryl, R₂ is aryl and Q is hydrogen or a groupwhich can be detached by reaction with the oxidized developer.

One group of yellow couplers are those compounds of the formula A inwhich R₁ is t-butyl and R₂ is a group of the formula

in which R₃ is hydrogen, halogen, alkyl or alkoxy and R₄, R₅ and R₆ arehydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl,alkoxycarbonyl, a carbamoyl group, a sulfone or sulfamoyl group, analkylsulfonamido group, acylamino group, ureido group or amino group.

Preferably, R₃ is chlorine, R₄ and R₅ are hydrogen and R₆ is anacrylamino group. This also includes the compounds of the formula

in which x is 0-4, R₇ is hydrogen or alkyl and R₈ and R₉ are alkyl.

Another group of yellow couplers is of the formula B

in which R₁₀ is hydrogen, halogen or alkoxy, R₁₁, R₁₂ and R₁₃ arehydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl,alkoxycarbonyl, a carbamoyl group, a sulfone group, sulfamoyl group,sulfonamido group, acylamino group, ureido group or amino group and R₁and Q are as defined above.

This includes compounds of the formula B in which R₁ is t-butyl, R₁₀ ischlorine, R₁₁ and R₁₃ are hydrogen and R₁₂ is alkoxycarbonyl.

In the compounds of the formula A and B the leaving group Q can behydrogen or it is a heterocyclic group

in which R₁₄ is a divalent organic group which completes the ring togive a 4-7-membered ring, or Q is a group —OR₁₅ in which R₁₅ is alkyl,aryl, acyl or a heterocyclic radical.

The yellow couplers are conventionally used in a quantity of 0.05-2 moland preferably 0.1-1 mol per mole of silver halide.

Examples of magenta couplers are simple 1-aryl-5-pyrazolones or pyrazolederivatives fused with 5-membered hetero rings, for exampleimidazopyrazoles, pyrazolopyrazoles, pyrazolotriazoles orpyrazolotetrazoles.

One group of magenta couplers comprises 5-pyrazolones of the formula C

as described in British Patent 2 003 473. In this formula R₁₆ ishydrogen, alkyl, aryl, alkenyl or a heterocyclic group. R₁₇ is hydrogen,alkyl, aryl, a heterocyclic group, an ester group, alkoxy group,alkylthio group, carboxyl group, arylamino group, acylamino group,(thio)urea group, (thio)carbamoyl group, guanidino group or sulfonamidogroup. R₁₇ is preferably a group

in which R₁₈ is imino, acylamino or ureido, R₁₉ is hydrogen, halogen,alkyl or alkoxy, R₂₀ is hydrogen, alkyl, acylamino, carbamoyl,sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group.

If Q′ is hydrogen, then the magenta coupler is tetraequivalent withrespect to the silver halide.

Typical examples of this type of magenta coupler are compounds of theformula

in which R₂₀ is as defined above and Q′, as described above, is aleaving group. These compounds are preferably in the material accordingto the invention.

Further examples of such tetraequivalent magenta couplers can be foundin U.S. Pat. Nos. 2,983,608, 3,061,432, 3,062,653, 3,127,269, 3,152,896,3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506,3,684,514, 3,834,908, 3,888,680, 3,891,445, 3,907,571, 3,928,044,3,930,861, 3,930,866 and 3,933,500 and in JP-A-89/309 058.

If Q′ in formula C is not hydrogen but a group which is eliminatedduring the reaction with the oxidized developer, then the magentacoupler is diequivalent. Q may in this case be, for example, halogen ora group which is attached to the pyrazole ring via O, S or N. Suchdiequivalent couplers give a higher colour density and are more reactivewith respect to the oxidized developer than the correspondingtetraequivalent magenta couplers.

Examples of diequivalent magenta couplers are described in U.S. Pat.Nos. 3,006,579, 3,419,391, 3,311,476, 3,432,521, 3,214,437, 4,032,346,3,701,783, 4,351,897, 3,227,554, in EP-A-133 503, DE-A-2 944 601,JP-A-78/34 044, 74/53 435, 74/53 436, 75/53 372 and 75/122 935.

2 pyrazolone rings can be linked via a divalent Q′, to give so-calledbis couplers. Examples of these are described in U.S. Pat. Nos.2,632,702, 2,618,864, GB-A-968 461, GB-A-786 859, JP-A-76/37 646, 59/4086, 69/16 110, 69/26 589, 74/37 854 and 74/29 638. Y is preferably anO-alkoxyarylthio group.

As mentioned above, pyrazoles fused with 5-memberedheterocycles—so-called pyrazoloazoles—can also be used as magentacouplers. Their advantages over simple pyrazoles are that they possesscolours with greater resistance to formalin and purer absorptionspectra.

Magenta couplers of the pyrazoloazole type, which are likewisepreferred, may be represented by the formula

in which R₁ is hydrogen or a substituent, Z represents the non-metallicatoms necessary to complete a 5-membered ring containing 2 or 3 nitrogenatoms, which ring may be substituted, and Q is hydrogen or a leavinggroup.

Among these, preferred magenta couplers are those of the formulae

R₁₁, R₁₂ and R₁₃ independently of one another are, for example,hydrogen, halogen, a group of the formula —CR₃ in which the radicals Rindependently of one another are hydrogen or alkyl, aryl, heterocyclyl,cyano, hydroxyl, nitro, carboxyl, amino, alkoxy, aryloxy, acylamino,alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio,alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl,alkoxycarbonyl, heterocyclyloxy, azo, acyloxy, carbamoyloxy, silyloxy,aryloxycarbonylamino, imido, heterocyclyl-thio, sulfinyl, phosphonyl,aryloxycarbonyl, acyl or azolyl, and preferably hydrogen; halogen (e.g.chlorine, bromine), a group of the formula —CR₃ in which the radicals Rindependently of one another are hydrogen or alkyl, aralkyl, alkenyl,alkynyl, cycloalkyl or cycloalkenyl and particularly preferably methyl,ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl,3-(3-pentadecylphenoxy)propyl,3-(4-(2-(4-(4-hydroxyphenylsulfonyl)phenoxy)dodecanamido)phenyl)propyl,2-ethoxytridecyl, trifluoromethyl, cyclopentyl,3-(2,4-di-t-amylphenoxy)propyl); aryl (e.g. phenyl, 4-t-butylphenyl,2,4-di-t-amylphenyl, 4-tetradecaneamidophenyl); heterocyclyl (e.g.2-furyl, 2-thienyl, 2-pyrimidyl, 2-benzothiazolyl); cyano; hydroxyl,nitro; carboxyl; amino; alkoxy (e.g. methoxy, ethoxy, 2-methoxyethoxy;2-dodecylethoxy, 2-methanesulfonylethoxy); aryloxy (e.g. phenoxy,2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy,3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); acylamino (e.g.acetoamido, benzamido, tetradecanamido,2-(2,4-di-t-amylphenoxy)butanamido,4-(3-t-butyl-4hydroxyphenoxy)butanamido,2-(4-(4-hydroxyphenylsulfonyl)phenoxy)decanamido); methylbutylamino);anilino (e.g. phenylamino, 2-chloroanilino,2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino,N-acetylanilino,2-chloro-5-(alpha-(3-t-butyl-4-hydroxyphenoxy)dodecanamidoanilino);ureido (e.g. phenylureido, methylureido, N,N-dibutylureido);sulfamoylamino (e.g. N,N-dipropylsulfamoylamino,N-methyl-N-decylsulfamoylamino); alkylthio (e.g. methylthio, octylthio,tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio,3-(4-t-butylphenoxy)propylthio); arylthio (e.g. phenylthio,2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,2-carboxyphenylthio, 4-tetradecanamidophenylthio); alkoxycarbonylamino(e.g. methoxycarbonylamino, tetradecyloxycarbonylamino); sulfonamido(e.g. methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido,p-toluenesulfonamido, octadecanesulfonamido,2-methyloxy-5-t-butylbenzenesulfonamido); carbamoyl (e.g.N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)-carbamoyl,N-methyl-N-dodecylcarbamoyl,N-(3-(2,4-di-t-amylphenoxy)propyl)-carbamoyl); sulfamoyl (e.g.N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl,N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl); sulfonyl (e.g.methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl);alkoxycarbonyl (e.g. methoxycarbonyl, butoxycarbonyl,dodecyloxycarbonyl, octadecyloxycarbonyl); heterocyclyl-oxy (e.g.1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy); azo (e.g. phenylazo,4-methoxyphenylazo, 4-pivaloylaminophenylazo,2-hydroxy-4-propanoylphenylazo); acyloxy (e.g. acetoxy); carbamoyloxy(e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy (e.g.trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino (e.g.phenoxycarbonylamino); imido (e.g. N-succinimido, N-phthalimido,3-octadecenylsuccinimido); heterocyclyl-thio (e.g. 2-benzothiazolylthio,2,4-diphenyloxy-1,3,5-triazole-6-thio, 2-pyridylthio); sulfinyl (e.g.dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfonyl);phosphonyl (e.g. phenoxy-phosphonyl octyloxyphosphonyl,phenylphosphonyl); aryloxycarbonyl (e.g. phenoxycarbonyl); acyl (e.g.acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl); azolyl (e.g.imidazolyl, pyrazolyl, 3-chloropyrazol-1-yl).

These substituents may if desired be substituted further, for example byhalogen or by an organic radical which is attached via a C, O, N or Satom.

The preferred groups R₁₁ are alkyl, aryl, alkoxy, aryloxy, alkylthio,ureido, urethane and acylamino groups.

R₁₂ can be as defined for R¹¹ and is preferably hydrogen, alkyl, aryl, aheterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acylor cyano.

R₁₃ can be as defined for R₁₁ and is preferably hydrogen, alkyl, aryl,heterocyclyl, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl,carbamoyl or acyl, preferably alkyl, aryl, heterocyclyl, alkylthio orarylthio.

Q is hydrogen or a leaving group such as halogen, alkoxy, aryloxy,acyloxy, alkyl- or arylsulfonyloxy, acylamino, alkyl- orarylsulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl, aryl- orheterocyclyl-S-carbamoylamino, a 5-membered or 6-memberednitrogen-containing heterocyclic radical, imido and arylazo. Thesegroups may if desired be further substituted as indicated for R₁₁.

Q is preferably halogen (e.g. fluorine, chlorine, bromine); alkoxy (e.g.ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy,methanesulfonylethoxy, ethoxycarbonylmethoxy); aryloxy (e.g.4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy,3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy); acyloxy(e.g. acetoxy, tetradecanoyloxy, benzoyloxy); alkyl- or arylsulfonyloxy(e.g. methanesulfonyloxy, toluenesulfonyloxy); acylamino (e.g.dichloroacetylamino, heptafluorobutyrylamino); alkyl- or arylsulfonamido(e.g. methanesulfonamido, trifluoromethanesulfonamido,p-toluenesulfonylamido); alkoxycarbonyloxy (e.g. ethoxycarbonyloxy,benzyloxycarbonyloxy); aryloxycarbonyloxy (e.g. phenoxycarbonyloxy);alkyl-, aryl- or heterocyclyl-S-(e.g. dodecylthio, 1-carboxydodecylthio,phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio);carbamoylamino (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino);5-membered or 6-membered nitrogen-containing ring (e.g. imidazolyl,pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl); imido(e.g. succinimido, hydantoinyl); arylazo (e.g. phenylazo,4-methoxyphenylazo).

Q can also form corresponding bis compounds by condensation of 4equivalents of coupler with an aldehyde or ketone. Q may also containphotographically active groups such as development inhibitors ordevelopment accelerators. Q is preferably halogen, alkoxy, aryloxy,alkylthio, arylthio or a 5-membered or 6-membered nitrogen-containingheterocyclic group which is attached to the coupling site via a nitrogenatom.

Pyrazolotetrazoles are described in JP-A-85/33 552; pyrazolo-pyrazolesin JP-A-85/43 695; pyrazolo-imidazoles in JP-A-85/35 732, JP-A-86/18 949and U.S. Pat. No. 4,500,630; pyrazolo-triazoles in JP-A-85/186 567,JP-A-86/47 957, JP-A-85/215 687, JP-A-85/197 688, JP-A-85/172 982,EP-A-119 860, EP-A-173 256, EP-A-178 789, EP-A-178 788 and in ResearchDisclosure 84/24 624.

Other pyrazoloazole magenta couplers are described in: JP-A-86/28 947,JP-A-85/140 241, JP-A-85/262 160, JP-A-85/213 937, JP-A-87/278 552,JP-A-87/279 340, JP-A-88/100 457, EP-A-177 765, EP-A-176 804, EP-A-170164, EP-A-164 130, EP-A-178 794, DE-A-3 516 996, DE-A-3 508 766 andResearch Disclosure 81/20 919, 84/24 531 and 85/25 758.

Cyan couplers may for example be derivatives of phenol, of 1-naphthol orof pyrazoloquinazolone. Structures of the formula E are preferred

in which R₂₁, R₂₂, R₂₃ and R₂₄ are hydrogen, halogen, alkyl, carbamoyl,amino, sulfonamido, phosphoramido or ureido. R₂₁ is preferably H or Cl,and R₂₂ is preferably an alkyl or amino group. R₂₃ is preferably anamino group and R₂₄ is preferably hydrogen. Q″ is hydrogen or a leavinggroup which is detached during the reaction with the oxidized developer.A detailed list of cyan couplers can be found in U.S. Pat. No.4,456,681.

Other examples of cyan couplers can be found in the following US-Adocuments: U.S. Pat. Nos. 2,369,929, 2,423,730, 2,434,272, 2,474,293,2,521,293, 2,521,908, 2,698,794, 2,706,684, 2,772,162, 2,801,171,2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,227,550, 3,253,294,3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,560, 3,476,563,3,516,831, 3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196,3,632,347, 3,652,286, 3,737,326, 3,758,308, 3,839,044, 3,880,661,4,004,929, 4,124,396, 4,333,999, 4,463,086, 4,456,681, 4,873,183 and4,923,791 and in EP-A-354 549 and EP-A-398 664.

The cyan couplers preferably employed in the red-sensitive silver halideemulsion layer of the material according to the invention are those ofthe formula

and/or of the formula

in which

Z₁ is alkyl or aryl, Z₂ is alkyl, cycloalkyl, aryl, a heterocyclic groupor a ballast group, Z₃ is hydrogen or halogen, Z₁ and Z₃ together mayform a ring, and Z₄ is hydrogen or a leaving group, and Z₅ is a ballastgroup, Z₆ is hydrogen or a leaving group and Z₇ is alkyl.

The colour developers conventionally used for colour-photographicmaterials are p-dialkylaminoanilines. Examples of these are4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline,4-amino-N-ethyl-N-α-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-α-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-α-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-α-methanesulfonamidoethylaniline,3-methyl-4-amino-N-ethyl-N-α-methoxyethylaniline,3-α-methanesulfonamidoethyl-4-amino-N,N-diethylaniline,3-methoxy-4-amino-N-ethyl-N-α-hydroxyethylaniline,3-methoxy-4-amino-N-ethyl-N-α-methoxyethylaniline,3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,N-dimethylaniline,N-ethyl-N-α-[α′-(α″-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline,N-ethyl-N-α-(α′-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and thesalts of such compounds, such as sulfates, hydrochlorides ortoluenesulfonates.

The UV absorbers of the formula Ib used in accordance with the inventioncan be incorporated alone or together with the colour coupler and, ifdesired, other additives into the colour-photographic material, bypredissolving them in high-boiling organic solvents. It is preferred touse solvents which boil at more than 160° C. Typical examples of suchsolvents are the esters of phthalic acid, phosphoric acid, citric acid,benzoic acid or of fatty acids, and alkylamides and phenols.

It is usual to use in addition a low-boiling solvent, in order tofacilitate the incorporation of the additives into thecolour-photographic material. Examples of such solvents are esters suchas ethyl acetate, alcohols such as butanol, ketones such as methylisobutyl ketone, chlorinated hydrocarbons such as methylene chloride, oramides such as dimethylformamide. Where the additives are themselvesliquid, they can be incorporated into the photographic material evenwithout the aid of solvents.

The UV absorbers according to the invention may if desired be dispersedin the gelatin layer without oil; Research Disclosure 88/296 017 and89/303 070.

Further details on high-boiling solvents which can be used can be foundin the following publications:

Phosphates: GB-A-791 219, BE-A-755 248, JP-A-76/76 739, 78/27 449,78/218 252, 78/97 573, 79/148 133, 82/216 177, 82/93 323 and 83/216.177and EP-A-265 296. Phthalates: GB-A-791 219, JP-A-77/98 050, 82/93 322,82/216 176, 82/218 251, 83/24 321, 83/45 699, 84/79 888.

Amides: GB-A-791 129, JP-A-76/105 043, 77/13 600, 77/61 089, 84/189 556,87/239 149, U.S. Pat. No. 928,741, EP-A-270 341, WO 88/00 723. Phenols:GB-A-820 329, FR-A-1 220 657, JP-A-69/69 946, 70/3 818, 75/123 026,75/82 078, 78/17 914, 78/21 166, 82/212 114 and 83/45 699.

Other oxygen-containing compounds: U.S. Pat. Nos. 3,748,141, 3,779,765,JP-A-73/75 126, 74/101 114, 74/10 115, 75/101 625, 76/76 740, 77/61 089,EP-A-304 810 and BE-A-826 039.

Other compounds: JP-A-72/115 369, 72/130 258, 73/127 521, 73/76 592,77/13 193, 77/36 294, 79/95 233, 91/2 748, 83/105 147 and ResearchDisclosure 82/21 918.

The quantity of high-boiling solvent is, for example, in the range from50 mg to 2 g per m² of support, preferably from 200 mg to 1 g per m².

Further preferred colour couplers for use in the compositions accordingto the invention, examples of such compounds, further additives such ascolour fogging inhibitors, DIR couplers and other light stabilizers suchas UV absorbers, phenols, phosphorus(III) compounds, organometalliccomplexes, hydroquinones and hydroquinone ethers, as well as moreprecise information on the structure of various photographic materials,can be taken from, for example, the publications U.S. Pat. No. 5,300,414and EP-A-520 938 and the literature cited therein.

The following examples describe the coating compositions according tothe invention in more detail without limiting the invention to theexamples. In these examples parts and percentages are by weight. Wherean example mentions room temperature, this should be understood asmeaning a temperature in the range 20-25° C., unless stated otherwise.

A) PREPARATION EXAMPLES

Examples A1 to A3 illustrate the preparation of starting materials.

Example A1

212.6 g (1.0 mol) of 98% 1,3-diphenyl-2-propen-1-one, 249.1 g (2.0 mol)of 98% guanidine nitrate and 1.51 of absolute ethanol are initiallyintroduced at 70° C. 289.2 g (4.0 mol) of 97% potassium methoxide arethen added in portions to the white suspension over the course of 40minutes. After 20 hours at reflux, the yellow suspension is cooled to50° C. and poured into 6 l of water, extracted with ethyl acetate, andconcentrated by evaporation and the residue is recrystallized fromisopropanol. 88.1 g of pale yellow crystals are obtained of the compound1

(=35.6% yield) with a melting point of 134-136° C.

Example A2

98.9 g (0.4 mol) of 2-amino-4,6-diphenyl-1,3-pyrimidine (compound 1) areintroduced into a solution consisting of 1.5 l of water and 1 l ofconcentrated sulfuric acid. A solution of 75.0 g (1.088 mol) of sodiumnitrite in 500 ml of water is added dropwise below the surface of theyellow suspension over the course of 25 hours. After 20 hours at 20-25°C. the yellow suspension is poured into 15 l of water and is renderedalkaline using 2.25 l of 25% aq. ammonia. The product precipitates as abeige solid. It is filtered off, washed with water and dried in a vacuumoven. 88.3 g (=88.9% yield) of beige crystals are obtained of theformula

with a melting point of 234-236° C.

Example A3

86.9 g (0.35 mol) of 2-hydroxy-4,6-diphenyl-1,3-pyrimidine (compound 2)are stirred in 400 ml (4.38 mol) of phosphoryl chloride under reflux for6 hours. The reaction mixture is cooled to 20-25° C. and added dropwiseto 4 l of water. The beige precipitate is filtered off, washed withwater and dried in a vacuum oven. 89.0 g (=95.4% yield) of beigecrystals are obtained of the formula

with a melting point of 112-114° C.

Examples A4 to A10 and A12 to A13 illustrate the preparation of thecompounds according to the invention.

Example A4

40 g (0.15 mol) of 2-chloro-4,6-diphenyl-1,3-pyrimidine (compound 3) areinitially introduced together with 22.5 g (0.165 mol) of 98% anhydrousaluminium chloride in 150 ml of a xylene isomer mixture at 70-75° C.20.0 g (0.18 mol) of 99% analytical-grade resorcinol are added inportions. After 25 hours at reflux, the reaction mixture is poured into1 l of water. The precipitate is washed with water and decanted. Theresidue is stirred with 1.5 l of hexane. The fine beige precipitate isfiltered off and dried. 46.9 g (=92% yield) of beige crystals areobtained of the formula

(compound 4) with a melting point of 225-228° C.

The following examples describe the preparation of compounds 5-10 of thegeneral formula

In these examples radicals R′ are defined as follows:

Compound 5:

Compound 6: R′=—OC₆H₁₃

Compound 7: R′=—O—CH₂—COOC₂H₅

Compound 8: R′=—O—CH(C₆H₁₃)—COOC₈H₁₇

Compound 9: R′=—O—CH₂—CH(OH)—CH₂—O—C₁₄H₂₉

Compound 10:

Example A5

3.4 g (0.01 mol) of2-(2′,4′-dihydroxyphenyl)-4,6-diphenyl-1,3-pyrimidine (compound 4) arestirred together with 2.1 g (0.011 mol) of 2-ethylhexyl glycidyl etherand 0.2 g (0.0005 mol) of ethyltriphenylphosphonium bromide for 30minutes at 150° C. The reaction mixture is cooled to 110° C. 25 ml oftoluene and 0.25 g of bleaching earth (Prolith Rapid®) are added theretoand the mixture is filtered while hot over kieselguhr. The clear yellowsolution is subjected to fractional filtration over silica gel 60(particle size 60-230 μm; Merck, Darmstadt), using toluene as eluent.

The clear yellow oil is stirred with hexane, the product crystallizingout. 3.8 g (=71.7% yield) of pale yellow crystals are obtained, m.p.67-69° C. (compound 5).

Example A6

6.0 ml (0.042 mol) of 1-bromohexane are added at room temperature to amixture of 13.6 g (0.04 mol) of compound 4, 5.8 g (0.042 mol) ofpotassium carbonate and 100 ml of DMF. The mixture is stirred at 130° C.for 5 hours, and is then cooled to room temperature and poured into 1 lof H₂O. The crystalline product is filtered off and recrystallized fromhexane. Compound 6 is obtained (R′=—OC₆H₁₃), m.p. 103-107° C.

Example A7

13.6 g (0.04 mol) of compound 4 are placed in 120 ml of absoluteethanol, and 11.2 g (0.10 mol) of potassium tert-butoxide are added. 8.5ml (0.08 mol) of ethyl chloroacetate are added to the yellow suspensionat 20° C. over the course of 5 minutes. The mixture is held at refluxtemperature with stiring for 24 h. After cooling to room temperature, itis poured into 1.5 l of H₂O. The crystalline product is filtered off andrecrystallized from ethanol. Compound 7 is obtained (R′=O—CH₂—COOC₂H₅),m.p. 138-140° C.

Example A8

6.8 g (0.02 mol) of compound 4 and 0.1 g of potassium iodide are addedat 110° C. to 2.8 g (0.02 mol) of potassium carbonate in 50 ml ofdiethylene glycol dimethyl ether (diglyme). 6.4 g (0.022 mol) of1-octyloxycarbonylheptyl bromide are added to the solution over thecourse of 20 minutes. The mixture is stirred at 120° C. for 7 h. Aftercooling to room temperature, the suspension is poured into 500 ml ofH₂O, the product is extracted with ethyl acetate and the organic phaseis evaporated. Compound 8 is obtained (R′=—O—CH(C₆H₁₃)—COOC₈H₁₇) as ayellow liquid. Mass spectrometry: M⁺=594 g/mol

Elemental analysis: calculated % C 76.7 found % C 76.1 % H 7.8 % H 7.9 %N 4.7 % N 4.6

Example A9

8.5 g (0.025 mol) of compound 4, 8.05 g (0.0275 mol) of tetradecylglycidyl ether and 0.46 g (0.00125 mol) of ethyltriphenylphosphoniumbromide are stirred at 150° C. for 3 hours. After cooling to roomtemperature, the clear, dark red melt is admixed with 15 ml of toluene.The catalyst is washed out with water. The product crystallizes slowly.Compound 9 is obtained (R′=—O—CH₂—CH(OH)—CH₂—O—C₄H₂₉) as a beigeproduct, melting point 68-69° C.

Elemental analysis: calculated % C 76.69 found % C 76.51 % H 8.25 % H8.28 % N 4.59 % N 4.59

Example A10

10.2 g (0.03 mol) of compound 4, 7.7 g (0.033 mol) of1,2,2,6,6-pentamethyl-4-(oxiran-2-ylmethoxy)piperidine and 0.56 g(0.0015 mol) of ethyltriphenylphosphonium bromide are stirred at 150° C.for 2.5 hours. After cooling to room temperature, the reaction mixtureis dissolved in 70 ml of ethyl acetate, subjected to a claifyingfiltration and concentrated by evaporation. The yellow solid obtained isrecrystallized from acetonitrile. Compound 10 is obtained

melting point 167-170° C.

Mass spectrometry: M⁺=568 g/mol; molecular weight 567.73 g/mol.

Elemental analysis: calculated % C 74.05 found % C 73.93 % H 7.28 % H7.34 % N 7.40 % N 7.37

Example A11 Preparation of Intermediates of the Formula

in which R′ is 4-methoxyphenyl (compound 11a) or in which R′ is Cl(compound 11b).

A solution of 4-methoxyphenylmagnesium bromide (prepared from 37.4 g[0.2 mol] of 4-bromoanisole and 4.9 g [0.2 mol] of iodine-activatedmagnesium turnings in 50 ml of tetrahydrofuran (THF)) is added dropwiseunder nitrogen and over the course of one hour to a solution of 18.3 g(=0.1 mol) of 2,4,6-trichloropyrimidine in 65 ml of anhydrous THF, thetemperature of the mixture being maintained within the range from 0 to20° C. After addition is complete the mixture is stirred at 20° C. for afurther 48 hours, and is then diluted with 90 ml of toluene and pouredinto 90 ml of 12% aqueous HCl. The organic phase is separated off,washed to neutrality with water and concentrated in a rotary evaporator.The brown oil obtained (34 g) is separated by column chromatography on500 g of SiO₂ (30-63 μm); the eluent is toluene/hexane, 60:40 to 100:0.Compounds 11a and 11b of the formula above are obtained;

2-chloro-4,6-bis(4-methoxyphenyl)pyrimidine (11a; R′=4-methoxyphenyl),melting point 187-189° C. and

2,4-dichloro-6-(4-methoxyphenyl)pyrimidine (11b; R′=Cl), melting point86-89° C.

Example A12

In analogy to the method described in Example A4, compound 11a obtainedin Example A11 is reacted with 1.2 equivalents of 99% analytical-graderesorcinol. Compound 12 of the formula

is obtained.

Example A13

In analogy to the method described in Example A4, compound 11b obtainedin Example A11 is reacted with 2.4 equivalents of 99% analytical-graderesorcinol. Compound 13 of the formula

is obtained.

B) APPLICATION EXAMPLES Example B1 Stabilization of a 2-coat MetallicFinish

The light stabilizers are incorporated into 5-10 g of xylene and testedin a clearcoat of the following composition:

Synthacryl ® SC 303¹⁾ 27.51 Synthacryl ® SC 370²⁾ 23.34 Maprenal ® MF650³⁾ 27.29 Butyl acetate/butanol (37:8) 4.33 Isobutanol 4.87 Solvesso ®150⁴⁾ 2.72 Kristallöl K-30⁵⁾ 8.74 Levelling assistant Baysilon ® MA⁶⁾1.20 100.00 g ¹⁾Acrylate resin from Hoechst AG; 65% solution in 26:9xylene/butanol ²⁾Acrylate resin from Hoechst AG; 75% solution inSolvesso ® 100⁴⁾ ³⁾Melamine resin from Hoechst AG; 55% solution inisobutanol ⁴⁾Manufactured by ESSO ⁵⁾Manufactured by Shell ⁶⁾Manufacturedby Bayer AG; 1% in Solvesso ® 150

2% of stabilizer is added to the clearcoat, based on the solids contentof the coating material. A number of additional coating samples areprepared which contain, in addition to the stabilizer according to theinvention, 0.7% of the compound

(compound A) based on the solids content of the coating material. Thecontrol is a clearcoat containing no light stabilizer.

The clearcoat is diluted to spray viscosity with Solvesso® 100 and issprayed onto an aluminium panel which has been pretreated (coil coat,filler, silver metallic basecoat) and baked at 130° C. for 30 minutes.The resulting dry film thickness of the clearcoat is 40-50 μm.

The samples are then weathered in a UVCON® weathering instrument fromAtlas Corp. (UVB-313 lamps) at a cycle of 8 h UV irradiation at 70° C.and 4 h condensation at 50° C.

The surface gloss (20° gloss in accordance with DIN 67 530) of thesamples is measured at regular intervals. The results of thesemeasurements are compiled in Table 1.

TABLE 1 20° gloss in accordance with DIN 67 530 before and afterweathering 20° gloss after weathering for Stabilizer 0 800 1200 16002000 2400 2800 3200 h none 90 67 21* 2% comp. 6 91 92 91 90 42* 2% comp.7 91 93 92 80 23* 2% comp. 8 91 92 92 89 35* 2% comp. 5 + 92 90 90 89 9090 89 83 0,7% A 2% comp. 6 + 90 93 91 90 91 91 91 78 0,7% A 2% comp. 7 +90 92 88 90 91 90 90 90 0,7% A 2% comp. 8 + 90 92 91 90 91 90 90 87 0,7%A *cracking

The stabilized sample has a better weathering stability (glossretention, crack resistance) than the non-stabilized comparison sample.

Example B2 Stabilization of Polycarbonate

10 g of polycarbonate powder (Lexan® 115) are dissolved with stirring atroom temperature in 50 g of methylene chloride, which requires severalhours. To this solution is added 0.2 g of UV absorber, corresponding to2% additional concentration. These solutions are used to cast films 20μm thick.

The films are exposed in an Atlas Weatherometer CI 65 at a black-paneltemperature of 63° C. and a relative humidity of 60%. Before beginningthe exposure experiments, the initial colour (YI_(AZ)) and subsequently,at regular intervals, the discolouration of the samples are tested bymeasuring the Yellowness Index (YI, method ASTM D 1925). Table 2indicates the initial colour (YI_(AZ)). The films are exposed furtheruntil they become brittle, which is evident by the formation of cracksin the films.

TABLE 2 Initial colour (Yellowness Index before weathering; YI_(AZ)) UVabsorber YI_(AZ) none 0.1 2% compound 6 0.4 2% compound 7 0.3

The samples stabilized with the compounds according to the inventionshow practically no discolourations in comparison with thenon-stabilized sample before the beginning of weathering. The exposureexperiments show that the substrate is given outstanding protectionagainst discolouration and embrittlement by the compounds according tothe invention.

Example B3 Inherent Stability in a Photographic Layer

43.7 mg of compound 5 are dissolved in 2 ml of ethyl acetate whichcontains tricresyl phosphate in a concentration of 24 g/l. 1 ml of thissolution is mixed with 9 ml of a solution containing, per liter, 27.6 gof gelatin and 6.8 g of an 8% aqueous solution of sodium4,8-diisobutylnaphthalene-2-sulfonate as wetting agent. The mixture ishomogeneously emulsified for 3 min in an ultrasound bath. Subsequently,7.5 ml of the resulting emulsion are mixed with 4.5 ml of an aqueouscuring solution comprising 0.24% of the potassium salt of2-hydroxy-4,6-dichloro-1,3,5-triazine. 8 ml in each case of thisemulsion are applied to polyester films with dimensions of 13×18 cm,corresponding to a UV absorber concentration of 0.467 g/m².

The samples are dried at room temperature for 7 days. The opticaldensity at the absorption maximum is then determined using a UV-VISspectrophotometer.

The samples are exposed in an Atlas Weatherometer CI 35 at a black-paneltemperature of 62° C. and a relative humidity of 50%. After an exposureduration corresponding to 60 kJ/cm² the optical density is againmeasured at unchanged wavelength, and the loss of optical density as aresult of exposure is determined from this measurement.

In the case of the sample stabilized with compound 5, the loss ofoptical density is 2.1%.

The stabilizer according to the invention thus possesses outstandinglight fastness in photographic layers.

Example B4 Stabilization of Polyamide

Polyamide 6 powder (Ultramid® B3S, manufactured by BASF) is mixed drytogether with stabilizers according to the invention for 2 minutes in aHenschel mixer and then processed in a Berstorff twin-screw extruder ata speed of 95/min and at a temperature setting of 230° C./235° C./240°C./240° C. The quantities of stabilizer are given in % by weight, basedon the quantity of polyamide employed. Using an injection moulding unit(model Arburg L, composition temperature 240° C., mould temperature 80°C.) 2 mm thick plates are produced from each mixture. For comparison, afurther sample is produced without stabilizers according to theinvention.

The plates are exposed in an Atlas Weatherometer CI 65 at a black-paneltemperature of 63° C. and a relative humidity of 60%, using a waterspray cycle of 102 min dry/18 min wet. The time for cracks to becomevisible on the plates is measured.

As well as the abovementioned stabilizers according to the invention,the following additional stabilizers are employed:

AN,N′-bis[3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionyl]hexamethylenediamine,

B tris(2,4-di-tert-butylphenyl)phosphite,

C the condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene-diamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine having a melting pointof 120-150° C.

The samples stabilized according to the invention show a very goodresistance to the appearance of cracks.

What is claimed is:
 1. A compound of the formula Ib

in which R¹ and R² independently of one another are H; OH; C₁-C₁₂alkyl;cyclohexyl or trifluoromethyl; R³ and R⁴ independently of one anotherare hydrogen; —OH; C₁-C₃alkyl; C₁-C₃alkoxy; or halogen or have one ofthe definitions of R⁷ or are OR⁷; R⁵ has one of the definitions givenfor R⁷ or is halogen; C₁-C₃alkyl; —O—CO—R¹²; —O—SO₂—R¹³ or —O—R⁷; R⁶ isH; C₂-C₁₈alkenyl; —X—Z³; benzoyl which is unsubstituted or substitutedon the phenyl ring by methyl, halogen, —CN or methoxy; —C(Z³)═N—Z³;—CH(Z³)—NH—Z³; a radical of the formula

 or a radical of the formula

R⁷ is C₄-C₁₈alkyl or C₂-C₁₈alkenyl or C₅-C₁₈alkyloxycarbonyl; or R⁷ isC₁-C₁₈alkyl which is substituted by a radical selected from the groupconsisting of OH, C₁-C₁₈alkoxy, C₂-C₁₈alkanoyl, halogen, —COOH, —COOR⁸,—CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰), —NHCOR¹¹, —CN,—OCOR¹¹, a radical of the formula

 and phenoxy which is unsubstituted or is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy or halogen; or R⁷ is C₄-C₂₀alkyl which is interrupted by Oand substituted by OH or C₁-C₁₂alkoxy; glycidyl; C₅-C₈cycloalkyl;cyclohexyl which is substituted by OH, C₁-C₄alkyl or —OCOR¹¹; orC₇-C₁₁-phenylalkyl which is unsubstituted or substituted by OH, Cl orCH₃; R⁸ is C₁-C₁₈alkyl; C₂-C₆-hydroxyalkyl; C₃-C₁₈alkenyl; C₃-C₂₀alkylwhich is interrupted by O, N or S and is unsubstituted or is substitutedby OH; C₁-C₄alkyl which is substituted by a radical selected from thegroup consisting of —P(O)(OR¹⁴)₂, —N(R⁹)(R¹⁰), —OCOR¹¹ and OH; glycidyl;cyclohexyl or C₇-C₁₁phenylalkyl; or is a group of the formula

R⁹ and R¹⁰ independently of one another are C₁-C₁₂alkyl;C₃-C₁₂alkoxyalkyl; C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂cycloalkyl or R⁹ andR¹⁰ together are C₃-C₉alkylene or -oxaalkylene or -azaalkylene; R¹¹ isC₁-C₁₈alkyl; C₂-C₁₈alkenyl or phenyl; R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl;phenyl; or —R¹⁵—O—CO—R¹¹; or is a group of the formula

R¹³ is C₁-C₁₂alkyl; phenyl; naphthyl or C₇-C₁₄alkylphenyl; and R¹⁴ isC₁-C₁₂alkyl or phenyl; R¹⁵ is C₁-C₁₈alkylene or C₂-C₁₈alkenylene; R¹⁶ ishydrogen; oxide; C₁-C₈alkanoyl; C₁-C₁₈alkyl; C₂-C₁₈hydroxyalkyl;C₃-C₁₈hydroxyalkyl which is interrupted by O; C₁-C₁₈-alkoxy;C₅-C₈cycloalkyl; C₅-C₈-cycloalkoxy; C₇-C₁₁phenylalkyl; C₇-C₁₁phenylalkylwhich is substituted on the phenyl ring by from 1 to 3 radicalsC₁-C₄alkyl or C₁-C₈alkanoyl; or C₇-C₁₁phenylalkoxy; X is a direct bondor —CO—; Z¹ and Z² independently of one another are C₁-C₁₂alkyl ortogether are C₄-C₁₀alkylene which may be interrupted by an oxygen atom;Z³ is C₁-C₂₀-Alkyl; and Z⁴ is hydrogen or methyl; with the exception ofa compound of the formula Ib in which 2 of the radicals R³, R⁴ and R⁵are alkoxy and the third radical has a definition other than alkoxy. 2.A compound of the formula Ib according to claim 1, in which R¹ and R²independently of one another are H; OH; C₁-C₁₂alkyl; cyclohexyl ortrifluoromethyl; R³ and R⁴ independently of one another are hydrogen;—OH; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; or halogen or may have one of thedefinitions of R⁷; R⁵ has one of the definitions given for R⁷ or ishalogen; —O—CO—R¹²; —O—SO₂—R¹³ or —O—R⁷; R⁶ is H or C₁-C₁₂alkyl; R⁷ isC₂-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which is substituted by a radicalselected from the group consisting of OH, C₁-C₁₈alkoxy, halogen, —COOH,—COOR⁸, —CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰),—NHCOR¹¹, —CN, —OCOR¹¹ and phenoxy which is unsubstituted or issubstituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy or halogen; or R⁷ isC₄-C₂₀alkyl which is interrupted by O and substituted by OH orC₁-C₁₂alkoxy; glycidyl; C₅-C₈cycloalkyl; cyclohexyl which is substitutedby OH, C₁-C₄alkyl or —OCOR¹¹; or C₇-C₁₁phenylalkyl which isunsubstituted or substituted by OH, Cl or CH₃; R⁸ is C₁-C₁₈alkyl;C₂-C₆hydroxyalkyl; C₃-C₁₈alkenyl; C₃-C₂₀alkyl which is interrupted by O,N or S and is unsubstituted or is substituted by OH; C₁-C₄alkyl which issubstituted by a radical selected from the group consisting of—P(O)(OR¹⁴)₂, —N(R⁹)(R¹⁰), —OCOR¹¹ and OH; glycidyl; cyclohexyl orC₇-C₁₁phenylalkyl; R⁹ and R¹⁰ independently of one another areC₁-C₁₂alkyl; C₃-C₁₂alkoxyalkyl; C₄-C₁₆-dialkylaminoalkyl orC₅-C₁₂cycloalkyl or R⁹ and R¹⁰ together are C₃-C₉alkylene or-oxaalkylene or -azaalkylene; R¹¹ is C₁-C₁₈alkyl; C₂-C₁₈alkenyl orphenyl; R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl; phenyl; or —R¹⁵—O—CO—R¹¹; oris a group of the formula

R¹³ is C₁-C₁₂alkyl; phenyl; naphthyl or C₇-C₁₄alkylphenyl; and R¹⁴ isC₁-C₁₂alkyl or phenyl; R¹⁵ is C₁-C₁₈alkylene or C₂-C₁₈alkenylene; R¹⁶ ishydrogen; C₁-C₈alkanoyl; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; C₅-C₈cycloalkyl;C₅-C₈cycloalkoxy; C₇-C₁₁phenylalkyl; C₇-C₁₁phenylalkyl which issubstituted on the phenyl ring by from 1 to 3 radicals C₁-C₄alkyl orC₁-C₈alkanoyl; or C₇-C₁₁phenylalkoxy; and X is a direct bond or —CO—. 3.A compound of the formula Ib according to claim 1, in which R¹ and R²independently of one another are hydrogen or C₁-C₄alkyl; R³ and R⁴independently of one another are hydrogen; C₁-C₃alkyl; C₁-C₃alkoxy orhalogen or have one of the definitions of R⁷ or are OR⁷; R⁵ has one ofthe definitions given for R⁷ or is halogen; —O—CO—R¹² or —O—R⁷; R⁶ is inthe o-position to R⁵ and in the p-position to —OH and is hydrogen,C₁-C₆alkyl, allyl, C₆-C₁₈alkanoyl, benzoyl or α-methylbenzyl; R⁷ isC₄-C₁₈alkyl or C₂-C₁₈alkenyl; or R⁷ is C₁-C₁₂alkyl which is substitutedby a radical selected from the group consisting of OH, C₁-C₁₈alkoxy,—COOR⁸, a radical of the formula

 and —OCOR¹¹; or R⁷ is C₇-C₁₈alkyl which is interrupted by from 1 to 6—O— and substituted by OH; C₅-C₈cycloalkyl; or C₇-C₁₁phenylalkyl; R⁸ isC₁-C₁₈alkyl; C₃-C₁₈alkenyl or a group of the formula

R¹¹ is C₁-C₁₈alkyl or C₂-C₁₈alkenyl; R¹² is C₁-C₁₈alkyl; C₂-C₁₈alkenyl;—R¹⁵—O—CO—CH═CH₂; or —R¹⁵—O—CO—C(CH₃)═CH₂; or is a group of the formula

R¹⁵ is C₂-C₁₈alkylene; and R¹⁶ is hydrogen; oxide; C₂-C₈alkanoyl;C₁-C₁₂alkyl; hydroxyethyl; C₁-C₁₈alkoxy; C₅-C₈cycloalkyl;C₅-C₈cycloalkoxy; or C₇-C₁₁phenylalkyl.
 4. A compound of the formula Ibaccording to claim 1, in which R¹ and R² independently of one anotherare hydrogen or C₁-C₄alkyl; R³ and R⁴ independently of one another arehydrogen or C₁-C₄alkoxy or C₁-C₄alkyl; R⁵ is —O—R⁷; R⁶ is in theo-position to R⁵ and in the p-position to OH and is hydrogen orC₁-C₆alkyl or allyl; R⁷ is C₄-C₁₈alkyl or C₃-C₁₈alkenyl; or R⁷ isC_(1 -C) ₁₂alkyl which is substituted by a radical selected from thegroup consisting of OH, C₁-C₁₈alkoxy, —COOR⁸, a radical of the formula

 and —OCOR¹¹; R⁸ is C₁-C₁₈alkyl; R¹¹ is C₁-C₁₈alkyl or C₂-C₃alkenyl. 5.A composition comprising A) an organic material which is sensitive todamage by light, oxygen and/or heat, and B) as stabilizer, a compound ofthe formula Ib according to claim
 1. 6. A composition according to claim5, in which component A is a photographic material or a thermoplasticpolymer which contains a heteroatom selected from nitrogen, oxygen andsulfur in the principal chain.
 7. A composition according to claim 6 inwhich component A is polycarbonate.
 8. A composition according to claim5 comprising from 0.01 to 15 parts by weight of component B per 100parts by weight of component A.
 9. A composition according to claim 5comprising, in addition to components A and B, another stabilizer orother additive.
 10. A method of stabilizing organic material againstdamage by light, oxygen and/or heat, which comprises adding to thismaterial a compound of the formula Ib according to claim 1 asstabilizer.
 11. A shaped article comprising A) a synthetic organicpolymer which is sensitive to damage by light, oxygen and/or heat, andB) a compound of the formula Ib according to claim
 1. 12. A shapedarticle according to claim 11 which is a multilayer system, wherein anexternal layer having a thickness of 10-100 μm comprises component (B)whereas the inner layer contains little or no compound of component(B).